WO2012094649A1 - Procédé de traitement par post-transestérification du biodiesel aboutissant à des fractions d'emag de grande pureté et à de nouveaux carburants - Google Patents

Procédé de traitement par post-transestérification du biodiesel aboutissant à des fractions d'emag de grande pureté et à de nouveaux carburants Download PDF

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WO2012094649A1
WO2012094649A1 PCT/US2012/020562 US2012020562W WO2012094649A1 WO 2012094649 A1 WO2012094649 A1 WO 2012094649A1 US 2012020562 W US2012020562 W US 2012020562W WO 2012094649 A1 WO2012094649 A1 WO 2012094649A1
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fame
fraction
biodiesel
fractions
methodology
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PCT/US2012/020562
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English (en)
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Duane Johnson
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Duane Johnson
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
    • Y02T50/678—Aviation using fuels of non-fossil origin

Definitions

  • the present invention may relate to various methodologies for the post- transesterification processing of biodiesel to obtain high purity fatty acid methyl ester (FAME) compounds. More particularly, the present invention may relate to those methodologies whose biodiesel fractionalization may use one or more crystallization-separation stages to generally obtain high purity, high yield FAME fractions, as well as utilizing the obtained FAME fractions to form new compositions.
  • FAME fatty acid methyl ester
  • Biodiesel may be used as an alternative fuel or an additive for combining with petroleum or fossil-based liquid fuels.
  • a typical use of biodiesel may be the replacement of or blending into Diesel #2, which itself is a crude mineral oil refining process distillate.
  • Diesel #2 may generally be used as fuel in internal combustion power plants used in vehicles, power generation equipment, and the like.
  • Biodiesel may be seen as a renewable, biodegradable, sustainable fuel (e.g., being obtained from replenishable sources such as oil seed crops and the like) that produces 85% less greenhouse gas emissions in comparison to non-renewable, generally non-biodegradable, petroleum-based Diesel #2 usage.
  • biodiesel may be further refined via hydrocracking to produce short-chain fatty acids and esters for use in turbine fuels.
  • a raw, renewable, source of fatty acids may be used as a feedstock (e.g., such as seed oil that is refined from crushing of seeds).
  • the biodiesel feedstock is a triglyceride (namely a glycerin molecule with 3 fatty acid carbon chains [generally of variable lengths] attached to it.)
  • Transesterification means known to those who have skill in the art, to react the triglyceride feedstock with an alcohol [e.g., methanol, ethanol, etc] in the presence of the base catalyst such as sodium hydroxide (NaOH) potassium hydroxide (KOH) or sodium methylate (NaOCH3).
  • the alcohol reacts with the fatty acids to form the mono-alkyl esters (or biodiesel) and crude glycerin (a/k/a glycerine, glycerol).
  • the mixture of mono-alkyl esters (or Fatty Acid Methyl Esters, also known by the acronym F.A.M.E. or FAME or other similar alkyl esters) and crude glycerin may then be substantially separated into a biodiesel (e.g., various FAME or mono-alkyl esters fractions) portion and a glycerin portion.
  • biodiesel fuel made from coconut oil has a very high Cloud Point and Gel Point in comparison to other biodiesel made from other feedstocks because it is primarily composed of saturated fatty acid esters.
  • biodiesel made from coconut oil feedstock may undergo a partial phase change at above acceptable temperatures leading to higher viscosity and crystallization, interfering with its use in engines, and possibly requiring the introduction of expensive gel point lowering additives into the resultant biodiesel.
  • Some feedstocks have high amounts of saturated fatty acids present giving their resulting biodiesel fuels improved oxidative stability, making the biodiesels less likely to require oxidative stabilization additives.
  • Such resulting biodiesel fuels are suitable in more tropical climates.
  • Biodiesel fuel manufactured from oils such as flax have a very different effect on biodiesel functionality.
  • Flax oil for example, is very high in highly unsaturated fatty acids (HUFA). Biodiesels made from such fatty acids have very low operating temperatures and can work under relatively cold conditions but are oxidatively unstable over time and in high heat conditions making them unsuitable for fuel use without excessive fuel stabilizers.
  • HUFA highly unsaturated fatty acids
  • Omega 3 FAME fractions may be classified as a member of the essential fatty acid group, so called because they cannot be produced within the human body and must be acquired through diet. Omega 3 FAME is shown to reduce serum cholesterol and is used in the neutraceutical industry in dietary supplements. Omega 3 FAME also may be highly sought out by the cosmetics industry as binders, as they are close in composition to skin oils.
  • ALA alpha-linolenic acid
  • the saturated and unsaturated FAME fractions may be used to provide a biodiesel with performance characteristics for a multitude of weather conditions, as well as be an additive for an aviation fuel, lubricant, or biodiesel blend, and heating oils.
  • Unsaturated FAME such as monounsaturated fatty acids (i.e., MUFA or omega 9) and polyunsaturated fatty acids (i.e., PUFA or omega 6) are typical of standards used by the European Union and North American FAMEs found in such a biodiesel feedstock per ASTM D6751 biodiesel test protocols.
  • the Omega 6 and Omega 9 FAME components found in the biodiesel may be more likely to undergo oxidation generating the presence of epoxies and ketones in the biodiesel.
  • the presence of these epoxies and ketones could require the use of stabilization additives in the biodiesel to allow it to function properly in its intended use.
  • the saturated FAME, having a high cloud point and the omega 3 (HUFA) generally having a poor oxidative stability are typically minimized to pass ASTM D6751 biodiesel fuel specifications.
  • One possible embodiment of the invention could be a methodology for separation and subsequent processing of FAME fractions of a biodiesel, comprising of the steps: providing a biodiesel containing several different FAME fractions mixed together, the biodiesel being at a first temperature wherein at the first temperature none of the FAME fractions of the biodiesel have crystallized; bringing the biodiesel to a first crystallizing temperature, wherein when the biodiesel reaches the first crystallizing temperature, a first FAME fraction remains in a non- crystallized, liquid phase while the remaining FAME fractions crystallize; and separating the liquid first FAME fraction from the remaining crystallized FAME fractions.
  • Another possible embodiment of the invention could be methodology for separating and subsequently processing of FAME fractions of biodiesel, comprising of the steps, providing a biodiesel that is a mixture containing at least several different FAME fractions, the biodiesel being at a first temperature wherein at the first temperature none of the FAME fractions of the biodiesel are crystallized; cooling the biodiesel from the first temperature to a first crystallization temperature, wherein a first FAME fraction is a liquid phase while the remaining FAME fractions are crystallized, allowing the first FAME fraction to be separated from the remaining crystallized FAME fractions; bringing the temperature of the remaining FAME fractions to a second crystallization temperature in which a second FAME fraction is crystallized while a third FAME fraction is in a liquid phase to allow the third FAME fraction to be separated from the second FAME fraction, wherein the first FAME fraction is Omega 3 FAME fraction, a second FAME fraction contains saturated FAME while third FAME fraction comprises of Omega 6 FAME
  • Another possible embodiment of the invention could be a methodology for separating and subsequently processing of FAME fractions of biodiesel, comprising of the steps, providing a biodiesel that is a mixture containing at least several different FAME fractions, the biodiesel being at a first temperature wherein at the first temperature none of the FAME fractions of the biodiesel have crystallized; cooling the biodiesel from the first temperature to a first crystallization temperature, wherein a first FAME fraction is a liquid phase while the remaining FAME fractions are crystallized, allowing the first FAME fraction to be separated from the remaining crystallized FAME fractions, wherein the first FAME fraction is Omega 3 FAME fraction; subjecting the first FAME fraction to glycero lysis to form Alpha-Linolenic Acid.
  • Another possible embodiment of the invention could be a methodology for separating and subsequently processing of FAME fractions of biodiesel, comprising of the steps, providing a biodiesel; sequentially cooling and heating of a biodiesel to provide for the repeated FAME fraction crystallization and subsequent separation of a first, second, and third FAME fractions of the biodiesel, wherein the first FAME fraction is an Omega 3 fraction, the second FAME fraction is saturated FAME fraction, and the third FAME fraction comprises of Omega 6 FAME and Omega 9 FAME; subjecting the third FAME fraction to hydrogenation to produce a mono unsaturated FAME; and performing hydrolysis of the mono-unsaturated FAME to create a first aviation jet fuel composition.
  • Another possible embodiment of the invention could be a methodology for separating and subsequently processing of FAME fractions of biodiesel, comprising of the steps, providing a biodiesel; sequentially cooling and heating of a biodiesel to provide for the repeated FAME fraction crystallization and subsequent separation of a first, second, third and fourth FAME fractions of the biodiesel, wherein the first FAME fraction is an Omega 3 fraction, a second FAME fraction having saturated FAME, and a third FAME fraction having Omega 6 FAME and Omega 9 FAME; subjecting the third FAME fraction to hydrogenation to produce a mono unsaturated FAME; performing hydrolysis of the Mono-unsaturated FAME to create a first aviation jet fuel composition; and adding the second FAME fraction to first aviation jet fuel composition to create a second aviation jet fuel composition.
  • Another possible embodiment of the invention could be a jet aviation fuel composition comprising percentage by volume: 1% C8; 1% C9 FAME; 31% C9; 31% CIO FAME; 6% CIO; 6% Cl l FAME; 4% Cl l; 0.5% C12 FAME; 0.1% C13 FAME; 0.5% C15 FAME; 10% C17 FAME; 4% C19 FAME; 2% C21 FAME; 1% C23 FAME; and 1% C25 FAME.
  • Another possible embodiment of the invention could be a jet aviation fuel composition comprising percentage by volume of 1% C8, 1% C9 FAME, 28% C9, 28% CIO FAME, 20% CIO, 20% Cl l FAME, 1% C12, and 1% C13 FAME.
  • Figure 1 is substantially a process block diagram of one methodology embodiment of the present invention.
  • Figure 2 is substantially a structural formula triglyceride molecule.
  • Figure 3 is substantially a chart of a selection of some of potential feedstock for the manufacture and refinement of biodiesel as used in the present invention.
  • Figure 4 is substantially a structural formulation of the chemical process for the transesterification process as generally used in the present invention.
  • Figure 5 is substantially a schematic showing a processing of crystallization and separation step of the invention.
  • Figure 6 is substantially a structural formulation of the chemical process for the glycerolysis process.
  • Figure 7 is substantially a schematic showing the hydrogenation step of the invention.
  • Figure 8 is substantially a schematic showing the hydrolysis step of the invention.
  • Figure 9 is substantially a chart showing an embodiment of the invention as a composition of a new fuel.
  • Figure 10 is substantially a chart comparing the characteristics of new fuel of the invention with those of existing jet fuels.
  • Figure 11 is substantially a chart showing the Pour Point of some Free Fatty Acids used to determine the temperature to separate FAME fractions.
  • the present invention 10 could comprise of a 100 methodology of post-transesterification high purity extraction from a biodiesel utilizing crystallization separation processes to generally obtain resultant high purity yields of various desired FAME fractions. These fractions are identified as FAME fractions and new fuels as process resultants 1 through 8 in Figure 1.
  • the process 100 could start with step 102, selection of the biodiesel feedstock having a preferred fatty acid profile.
  • the operator could look for that feedstock whose triglyceride molecules have a fatty acid profile high in those components that the operator wishes to obtain in high purity high yield fractions for their own commercial use or to be used as fuel additives or fuel base for the formulation of new fuels and the like.
  • each R represents a hydrocarbon chain of eight (8) to twenty-four (24) carbon atoms, but the lengths of Rl, R2, and R3 are not necessarily equal.
  • Figure 3 substantially shows a Fatty Acid Profile Chart that generally shows the percentage of fatty acids and their carbon chain length (via the triglyceride molecule) that may be associated with some oils as set forth in the "Feedstock” column that may be used as biodiesel feed stock.
  • This table should be only considered to be merely exemplary and not all to an inclusive listing of potential feedstock for biodiesel production (other biodiesel feedstocks being organic waste oils, algae-based products, and the like.)
  • the number after the "C” is the length of the carbon chain.
  • the number after the semicolon is the number of double bonds in the carbon chain.
  • those fatty acids whose chains that lack double bonds are generally considered “saturated” fatty acids (all of their bonds being single bonds.)
  • Those fatty acid chains with only one double bond or an "unsaturated” bond are generally considered “mono unsaturated” fatty acids (e.g., one such a nine [9] carbon fatty acid chain with a single double bond is known as Omega 9 fatty acid or MUFA).
  • Omega 9 fatty acid or MUFA Omega 9 fatty acid
  • the fatty acids whose hydrocarbon chains have multiple double bonds are generally marked as "polyunsaturated” fatty acids or PUFA.
  • Such examples of these "polyunsaturated" fatty acids could be the Omega 6 fatty acids (i.e., a hydrocarbon chain unsaturated at position 6 distal to carboxyl group) and Omega 3 fatty acid (i.e., a hydrocarbon chain unsaturated at position 3 distal to the carboxyl group).
  • Omega 6 fatty acids i.e., a hydrocarbon chain unsaturated at position 6 distal to carboxyl group
  • Omega 3 fatty acid i.e., a hydrocarbon chain unsaturated at position 3 distal to the carboxyl group
  • One such Omega 3 polyunsaturated fatty acid chain is the CI 8:3, which is also known as Alpha Linolenic Acid (or ALA).
  • the resulting FAME or biodiesel could have a Fatty Acid profile significantly different from the original feedstock triglyceride (except that the resultant FAME includes an Alcohol bonded in lieu of the glycerine backbone as part of the transesterification process).
  • the Biodiesel (generally composed of multiple FAME fractions) can be made from any oil or fat on the list (as well as many other feedstocks not shown on the lists).
  • the invention 10 can be used to isolate one or more specific FAME fractions, the operator could reference the list to select an oil feedstock that contains relatively high amounts of certain Fatty Acid(s) that could give rise through the invention of corresponding specific and desired, high yield, high purity FAME fraction(s).
  • Camelina oil is generally very high in the C18:3n3 (Omega 3) fatty acid (e.g., for clarification of the nomenclature, the "CI 8" denotes that the fatty acid has a carbon chain of 18 carbons while the “3” denotes three double bonds on the chain.)
  • the n3 denotes this is an Omega 3 with the double bond at the third position distal to the carboxyl group and therefore could be considered a very good seed oil feedstock to form a biodiesel from which the invention 10 could subsequently refine and isolate Omega 3 FAME fraction.
  • the invention 10 could also refine and purify from biodiesel the Omega 6 FAME and Omega 9 FAME (as well as other FAME fractions) and then substantially further process those FAME fractions into a new fuel that could have an optimal use as an aviation fuel.
  • Jatropha, Canola, Safflower, Sunflower and Soy oils could be very good feedstock choices to generally optimize this portion of the invention 10 because each these feed stock choices has a high combined sum of primarily C18: ln9 fatty acids (e.g., forming resultant Omega 9 FAME-having 18 carbon chain with one double bond in the carbon chain at the nine (9) carbon position) and C18:2n6 fatty acids (e.g., forming resultant Omega 6 FAME- having 2 double bonds in the hydrocarbon chain at the nine [9] position and at the six [6] position of distal end).
  • C18: ln9 fatty acids e.g., forming resultant Omega 9 FAME-having 18 carbon chain with one double bond in the carbon chain at the nine (9) carbon position
  • C18:2n6 fatty acids e.g., forming resultant Omega 6 FAME- having 2 double bonds in the hydrocarbon chain at the nine [9] position and at the six [6] position of distal end.
  • step 104 transesterification As substantially shown in Figure 4, step 104 transesterification, as generally set forth above, this portion of the process may include the preparation steps as known by those with ordinary skill in the art for the formation of biodiesel (e.g., saponification and subsequent removal of free fatty acids in the feed stock; removal of excess water, general contaminate removal or amelioration; and the like).
  • the prepared feed stock may then placed into a generally enclosed chamber or the like where the triglyceride feedstock is substantially reacted with a base catalyst (e.g., such as an organic salt or alkoxide like potassium or sodium methylate) and alcohol (e.g., methanol) to generally form a mixture substantially comprised of glycerol portion and a biodiesel portion generally made up of various FAME compounds.
  • a base catalyst e.g., such as an organic salt or alkoxide like potassium or sodium methylate
  • alcohol e.g., methanol
  • the mixture can subsequently be subject to various techniques and equipment to substantially provide either both batch and high volume separation of the Biodiesel (FAME) portion from the glycerine/glycerol portion.
  • FAME Biodiesel
  • Commercial/large scale processing equipment for implementing this stage is available from Green Fuels Ltd. of the United Kingdom.
  • step 106 FAME purification, various processes and apparatuses can be applied to the separate biodiesel (FAME) portion to generally remove unwanted byproducts, soap, glycerin, excess alcohol, and trace amounts of water that occurred in the transesterification process.
  • FAME biodiesel
  • steps 102, 104, and 106 could be bypassed, with the procurement of commercially available biodiesel meeting ASTM D6751 standard (e.g., commercial grade biodiesel).
  • ASTM D6751 standard e.g., commercial grade biodiesel
  • the limitation to such an embodiment could be the probable inability of the operator to procure a commercial grade biodiesel made from a specific feedstock or feedstock combination designed to maximize the output of the invention process to obtain in desired yields the desired FAME fractions to meet the needed quantities as fuel base and/or additive for the invention 10.
  • step 106 the process 100 could proceed to step 108, first crystallization-separation.
  • the specifically created biodiesel (using feedstock specifically selected to provide significant quantities of certain FAME fractions of FAME at the expense of other FAME fractions) will crystallize various FAME fractions at various temperatures proximate to or below freezing based on physical properties imbued by the length of the hydrocarbon chain of the particular FAME fraction. This phenomenon substantially allows for separation of various FAME fractions constituting a specific feed stock based biodiesel.
  • Omega 3 e.g., the highly polyunsaturated FAME would crystallize at -11°C while Omega 6 FAME, Omega 9 FAME, and Saturated FAMEs will crystallize at -5°C, 0°C, and 5°C respectively.
  • Figure 11 further shows the Pour Points (or crystallization points) of various Free Fatty Acids.
  • the crystallization separation step could be a two- phase process involving a crystallization phase/apparatus and a separation phase/apparatus.
  • the apparatus could involve a refrigeration/freezing unit and heat exchanger having the ability to drop the flow of FAME moving through the unit down to minus 8°C. At this temperature, the Omega 6 FAME, Omega 9 FAME, and saturated FAME should crystallize while leaving the Omega 3 as a liquid.
  • the mixture of the crystallized fractions of FAME (together) and the liquid Omega 3 FAME fraction could have significantly different and distinguishable characteristics (e.g., different respective densities allowing for a density gradient separation, different sizes for filtration-based separation)
  • the second phase of separation can provide for the refrigerated biodiesel to be processed through centrifuge, membrane filters, or other suitable separation means to separate and remove the liquid fraction from the crystallized fractions based on density differentiation.
  • the separation and removal of the liquid phase Omega 3 FAME component from the remaining crystallized fractions of biodiesel could result in the Omega 3 FAME fraction having 85-90 percent purity.
  • the Omega 3 FAME can be converted back into an Omega 3 triglyceride in process 109 called glycero lysis. Stated simply, this is the reverse process to transesterification, where the alcohol molecule is generally removed from the Omega 3 FAME. In many cases, this is the form of Omega 3 that the nutrition and cosmetics market want to purchase.
  • the glycerolysis reaction may use Omega 3 FAME and crude glycerol as inputs to generally yield Omega 3 triglyceride and alcohol.
  • step 108 the removal of the Omega 3 FAME from the remaining fractions of biodiesel at step 108 could increase the oxidative stability of remaining biodiesel/FAME fractions when used as a fuel.
  • step 108 the process 200 could proceed to step 110, 2 nd crystallization-separation of those remaining Omega 6, Omega 9, & Saturated FAME fractions.
  • this step 110 the 2 nd crystallization-separation, the remainder biodiesel FAME fractions of the I s processed through this crystallization-separation step utilizing wherein the remainder fraction is generally chilled to 5°C to crystallize the saturated FAME fraction, leaving the Omega 6 FAME and Omega 9 FAME fractions substantially in a liquid phase.
  • the remainder biodiesel can then be moved through the separation phase to separate out the crystallized saturated FAME fraction from the combined Omega 6 and Omega 9 FAME fraction in liquid phase.
  • the inventor generally estimates that if the Camelina oil-based biodiesel is used, the separated saturated FAME substantially represents about 12% of the original biodiesel by volume while the separated Omega 6 and 9 FAME fractions could respectively represent approximately 36% and 19% of the original biodiesel by volume.
  • the remaining Omega 6 and 9 FAME fractions could be run through a heating means to return them from a crystallized state to a liquid state.
  • step 110 Once step 110 has been completed, the process 100 could move onto step 112, hydrogenation.
  • step 110 could have the combination containing Omega 6 and Omega 9 FAMEs that could be subject to a hydrogenation process as known by those skilled in the art.
  • the Omega 6 FAME fraction could represents 65% of the remaining mixture by volume, the balance generally being Omega 9 FAME fraction.
  • the remaining FAME fractions mixture may be sent or sprayed into a reactor, which may contain a hydrogen gas atmosphere (at 2-3 atmospheric pressure), heated to 100°C temperature, and a solid nickel catalyst.
  • the hydrogenation reaction may generally occur first at a distal unsaturated point (e.g., at the six [6] carbon double bond, converting it to single bond) away from the carboxyl group, creating a preferential conversion of Omega 6 FAME (C18:2n6) to Omega 9 FAME (C18: ln9), this conversion substantially occurring prior to any conversion of Omega 9 FAME (CI 8: 1) to a saturated FAME (CI 8).
  • CI 8 Omega 9 FAME
  • the operator if so desirous, could control the hydrogenation to allow it to generally continue and further convert the double bond at the 9 position of both FAME fractions to a single bond so that both FAME fractions are then converted to fully saturated (i.e., no double bonds) FAME, if such a FAME fraction was desired.
  • the duration of hydrogenation can be seen as varying the overall FAME composition of the remaining fractions as desired by the operator.
  • step 114 hydrolysis could have the resultant Omega 9 FAME fraction transferred to a hydrolysis reactor and mixed with water, the combined water- Omega 9 FAME mixture is subject to five (5) atmospheres of pressure and to temperatures generally at 120°C for a period of 24 hours to fracture its carbon chain at the unsaturated number nine (9) position double bond of the Omega 9 FAME.
  • This fraction's hydrocarbon chain could fracture at the unsaturated site into two fragments: an oxygenated nine- carbon fragment with the attached methyl ester group and a saturated carbon chain making up the balance of the former fatty acid. Chain length of this second carbon polymer could vary depending upon the original FAME molecule.
  • the resultant mixture could be comprised of nine (9)-carbon hydrocarbon chains having a methyl group at one end (i.e., a methylated 9-carbon chain) and nine (9)-carbon hydrocarbon chains without a methyl group.
  • the reacting of a fraction of a 20: 1 FAME could result (depending on the location of the single double bond) in the generation of a mixture of a methylated ten (10) carbon chains and ten (10) carbon chains.
  • the resultant fraction mixture being ultimately directed by the feedstock used to create the original biodiesel.
  • This new fuel may be seen as being compatible to the compositions of Jet A, Jet Al, and JP8 aviation fuels in that they generally have a primary ingredient of "nonane"- a linear alkane hydrocarbon with the chemical formula of C9H20 that is principally derived from petroleum but structurally similar to the carbon fragments derived from the invention's process described above.
  • Conventional fuel that is based on nonane is typically classified as kerosene.
  • the hydrolysis process of the invention by cleaving the Omega 9 FAME at the nine carbon double bond position substantially creates a fuel similar in composition to conventional jet fuel with the exception that 50% of the fuel has half its nine carbon chains being oxygenated hydrocarbon (e.g., have a methyl group).
  • This new fuel in comparison to the established jet fuel should have the characteristic of reducing emissions in that more oxygen in the new fuel should lead to cleaner fuel consumption and a reduced cloud point.
  • the new fuel, in containing longer carbon fragments than normally found in the established jet fuels, should be able to restore any energy potential lost in having the oxygenated fragments.
  • step 114 Once step 114 is completed, the process could substantially proceed to step 116, mixing process.
  • step 116 mixing process, the new aviation fuel of the invention obtained in step 114, may be mixed with an additive of the third (saturated) FAME fraction that was originally isolated in step 110.
  • This new mixture may form a new second fuel to contain C9-11, C9- 11+Me, and saturated FAME.
  • This new fuel mixture generally represents 67% of the original biodiesel of the Camelina oil feedstock.
  • the composition of the New Fuels (Items 7 and 8) are shown in Figure 9.
  • Figure 10 substantially shows the characteristics of New Fuel (Item 7) vs. existing Jet Fuels.

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Abstract

La présente invention concerne un procédé de séparation et de prise en charge ultérieure des fractions d'ester méthylique d'acides gras (EMAG) du biodiesel, comprenant les étapes consistant à fournir un biodiesel contenant plusieurs fractions différentes d'EMAG mélangées ensemble, le biodiesel se trouvant à une première température à laquelle aucune des fractions d'EMAG du biodiesel n'a cristallisé; porter le biodiesel à une première température de cristallisation, à laquelle une première fraction d'EMAG reste en phase liquide non cristallisée tandis que les fractions d'EMAG restantes cristallisent; et séparer la première fraction d'EMAG liquide des fractions d'EMAG cristallisées restantes.
PCT/US2012/020562 2011-01-06 2012-01-06 Procédé de traitement par post-transestérification du biodiesel aboutissant à des fractions d'emag de grande pureté et à de nouveaux carburants WO2012094649A1 (fr)

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US201161430424P 2011-01-06 2011-01-06
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